Diazotype material



United States Patent 20 Claims. (or. 9649) The invention relates todiazotype material of the socalled one-component type, which contains ap-amino benzene diazo compound, derived from a tertiary aromatic aminehaving only one aryl radical attached directly to the tertiary nitrogenatom, which compound in the para-position carries the diazo group and inone of the ortho-positions an etherified hydroxyl group.

This application is a continuation-impart of our copending US.application Ser. No. 851,968, filed Nov. 10, 1959, now abandoned.

As is known, the light-sensitive diazo compounds used in positivediazotype material are converted by irradiation with actinic light intocompounds which are only slightly coloured, if at all, hereinaftercalled light-decomposition products. The diazo compound left in thediazotype material after the imagewise exposure is converted into anazo-dyestutf during the so-called development following the imagewiseexposure, by reaction with an azo-dyestuff component. Thelight-decomposition products present in the exposed portions do not forman azo-dyestuif with the azo-dyestuff component. The diazo compounds andazodyestutf components or mixtures of diazo compounds and/or mixtures ofazo-dyestulf components preferably selected are those which formazo-dyestuffs producinggood contrasts, e.g. dark, such as blue or black,azo-dyestuffs.

In the practice of the diazotype process very many copies, e.g. oftransparent pencil drawings and letters are produced with a so-calledfoggy background.

After the imagewise exposure these copies, even in the most exposedportions, still contain (besides a relatively large quantity oflight-decomposition products) a small quantity of diazo compound, whichis converted into a corresponding small quantity of dyestuff duringdevelopment. Except in some cases, in which special effects are aimedat, it is generally desirable for the dyestutf to have the same colourin all the image portions of the developed diazotype copy. It may havean extremely disturbing effect if the dyestuff in the foggy backgroundof the copy shows a colour differing from that of the dyestuff in theimage portions that have been only slightly exposed, if at all,especially if that colour, instead of pure blue or pure black, is animpure blue or an impure black owing to the presence of a reddish orviolet shade. Such impure colours are called off-shades.

Belgian Patent No. 564,343 describes a process in which diazotypematerial is used which contains a diazo compound of the type in which Rrepresents an alkyl group with at most 4 carbon atoms and R representsan alkyl group with at most 4 carbon atoms or an aralkyl group with atmost 7 carbon atoms, and in which R represents an alkyl group with atmost 4 carbon atoms.

The diazo compounds of this type are very sensitive to the light of themercury-vapour lamps that are frequently 3,397,058 Patented Aug. 13,1968 employed in the diazotype process, both of the high-pressure lampsand of the low-pressure lamps, and both of the actinically fluorescentand of the non-fluorescent lamps.

Diazotype material sensitized with diazo compounds of this type isextremely suitable for the visual observation of the endpoint of theexposure in the process of copying in the light of actinicallyfluorescent mercury-vapour lamps.

Many of the diazo compounds mentioned in Belgian Patent No. 564,343yield dark azo-dyestuffs, producing good contrasts, with the azocomponents commonly used in the diazotype process, such asphloroglucinol, 2,3-dihydroxynaphthalene and its derivatives,2,3-hydroxynaphthoic acid amides and 2-naphthal-3,6-disulphonic acid.

In respect to both light-sensitivity and suitability for visualobservation of the endpoint of the exposure, diazotype materialsensitized with diazo compounds of this type is quite different from thecommonly used diazotype material sensitized with p-tert. aminobenzenediazo compounds having no alkoxy group ortho to the tert. amino group.The latter diazotype material is much less lightsensitive andpractically is not suited for the visual observation of the endpoint ofthe exposure.

Copies on diazotype material as described in the said Belgian patent,however, often show off-shades in the image portions, in which after theimagewise exposure both the diazo compound and the light-decompositionproducts are present, e.g. in the foggy background. The off-shades areespecially objectionable when the diazo compound has been converted intoa blue or black azodyestuff during development. It has been found thatduring development both the light-decomposition products and theazo-dyestuff component form dyestutf in the portions in which they arepresent simultaneously with the diazo compound, so that in thoseportions mixtures are produced of azo-dyestutf formed by theazo-dyestuff component with dyestuif formed by the light-decompositionproducts. The latter dyestulf often has a reddish or violet shade, whichforms an impurity for the pure colour of the azo-dyestuff formed fromthe azo-dyestuff component.

Moreover, the azo-dyestuffs of copies on diazotype material according tothe said Belgian patent often show an undesirable change of colour inconsequence of a decrease of pH occurring in the surface of thediazotype copies. The said surface may turn acid or more acid, either10- cally, e.g. by spilling of acid liquids, or all over, e.g. when thecopies are kept in a humid atmosphere, owing to which the acid from theinterior of the paper (as is known, basepaper for the diazotype processoften contains comparatively large quantities of acid, e.g. in the formof alum) can diffuse to the surface.

Besides the diazo compounds mentioned in the said Belgian patent, thereare corresponding compounds having a chlorine atom, a methyl group or anethoxy group in the para-position with respect to the alkoxy group. Someof these compounds are disclosed in a copending application Ser. No.815,781, now US. Patent No. 3,169,869, filed after the priority date ofthe present application. The compounds 4-diazo-2,5-diethoxy phenylmorpholine and 4-diazo-2,5-diethoxy phenyl piperidine are known. Thesediazo compounds are also very light-sensitive but when diazotypematerial is manufactured with these diazo compounds, the azo-dyestuffsof copies on such diazotype material are often found to show anundesirable change of colour owing to a decrease of the pH. Offshades inthe incompletely exposed portions of the copies are also frequentlyobtained, especially when the chloro compounds are used.

Some of the above-mentioned very light-sensitive diazo compounds havesuch a low coupling activity that they are suited only for themanufacture of two-component diazotype material which is developed byexposure to ammonia vapour. Some of them have a greater couplingactivity so that they are suited for the manufacture of one-componentdiazotype material which is developed by means of an alkaline-reactingdeveloping liquid. None of those compounds, however, is suited for themanufacture of onecomponent diazotype material to be developed by meansof an acid-reacting developing liquid. As is well known in the diazotypeart, acid-reacting developing liquids are more stable than thealkaline-reacting developing liquids. So the impracticability of usingthe former involves a very important practical disadvantage.

It is an object of the present invention to provide a material whichobviates the above-mentioned disadvantages.

It is a further object of the present invention to provide a verylight-sensitive one-component diazotype material which can be developedsatisfactorily by means of an acid-reacting developing liquid.

The one-component diazotype material according to the present inventioncomprises a support sensitized with a light-sensitive compositioncontaining, in the absence of an aZo-coupling component, alight-sensitive diazo compound of the formula in which /Rr N is selectedfrom the class consisting of dialkylamino groups, N-ethyl N-benzylaminogroups, N-alkyl-N-cyclohexylamino groups, (alkyl) (acyloxyalkyDaminegroups, di(acyloxyalkyl)amino groups (in which groups the alkyl andbenzyl radicals may carry further substituents) and the morpholino ring;R is a phenyl group, either substituted or unsubstituted; X is an anionand Y is selected from the class consisting of hydrogen and halogenatoms.

The aforesaid diazo compounds are new chemical compounds per se. Theirlight-decomposition products which are present, after the imagewiseexposure, in the exposed image portions of copies on diazotype materialaccord ing to the present invention, form, during development, hardlyany undesirable dyestuffs with diazo compound still present in thoseimage portions. The azo-dyestuffs of copies on diazotype materialaccording to the present invention are highly resistant to a decrease ofthe pH.

The diazotype material according to the present invention additionallypossesses the above-mentioned good properties possessed by the diazotypematerial used in the process of Belgian Patent No. 564,343. In using thediazotype material of the Belgian patent it appears that the formationof off-shades is affected by the choice of the azo-dyestuif componentsand by the choice of the medium in which the formation of azo-dyestulftakes place. The azo-dyestulf component 2,3-hydr0xynaphthoic acid-18-hydroxyethylamide, if used in an alkaline-reacting developing liquid,causes more serious ofi-shades than does phloroglucinol in analkaline-reacting developer. Phloroglucinol in a developer with an acidreaction causes more serious off-shades than does phloroglucinol in analkaline-reacting developer.

When diazotype material according to the present invention is used,copies with hardly any off-shades are obtained in all these cases. Thediazo compounds and the dyestuff components of course have to beselected in such a way that their coupling activity is sufficient forthe medium in which the formation of azo-dyestuff takes place.

Diazotype material according to the present invention which contains adiazo compound in which the amino group carries a benzyl group and analkyl group is suitable for development with weakly acid, bufferedphloroglucinol developers. As is known, these developers in general havebetter resistance to oxidation than alkaline phloroglucinol developers.Copies on this material developed in such a way do not show off-shadesowing to dyestufi formation by the light-decomposition products.

The diazo compounds which are used in the diazotype material accordingto the present invention also include compounds in which, besides thediazo group, the amino group and the phenoxy or substituted phenoxygroup, the benzene nucleus carrying the diazo group carries yet anothersubstituent, such as a halogen atom, in the paraposition with respect tothe phenoxy or substituted phenoxy group.

Diazotype material according to the invention which contains a diazocompound in which the amino group carries a benzyl group and an alkylgroup, and in which the benzene nucleus carrying the diazo group carriesa chlorine atom in the para-position with respect to the phenoxy orsubstituted phenoxy group, is also very attractive. Owing to the greatcoupling activity .of the said diazo compound this diazotype material isespecially suitable for development with weakly acid, buiferedphloroglucinol developers, e.g. according to the so-called semi-wetprocess, in which a uniform thin layer of the developing liquid of, forexample 8 g./m. is applied on the irnagewise exposed material. Copies onthis material developed in such a way do not show off-shades owing todyestufl formation by the light-decomposition products.

In the diazo compounds which are used in the diazotype materialaccording to the present invention the phenoxy group may carry one ormore substituents. Such substituents are halogen atoms, alkoxy groups,methyl groups, monoand dialkylamino groups and others. Diazotypematerial containing a diazo compound in which the phenoxy group carriesat least one chlorine atom, shows a greater speed of development thancorresponding material containing the corresponding diazo compound withan unsubstituted phenoxy group.

The alkyl groups in the amino group may also carry substituents such ashydroxy, alkoxy, acyloxy, chloro, acylamino etc. Diazotype materialcontaining a diazo compound in which the amino group carries twoacyloxyalkyl groups e.g. two acetyloxyethyl groups couples more activelyupon development with a weakly acid buffered phloroglucinol developerthan does corresponding diazotype material containing a diazo compoundhaving the same structure but for the presence of two ethyl groups inthe amino group. Further suitable acyloxy groups are: propionyloxy,butyryloxy, phenacetyloxy, chloroacetyloxy, benzoyloxy, furoyloxy,ethoxycarbonyloxy, phenylamidocarboxyloxy and methylsulphonyloxy groups.

Besides those mentioned in the examples which follow, the followingdiazo compounds may be especially mentioned as diazo compounds which mayserve for the manufacture of diazotype material according to the presentinvention:

4-diethylamino-3-o-diethylaminophenoxy benzene diazonium borofiuoridedouble salt,

4 N methyl-N-benzylamino-3-phenoxy-6-fluorobenzene diazoniump-chlorobenzene sulphonate,

4-dimethylamino-3-phenoxy-6 bromobenzene diazonium chloride, zincchloride double salt,

4-N-hydroxyethyl-N-o, p-dibromobenzylamino3-p-chlorophenoxy-6-chlorobenzene diazonium chloride, stannic chloridedouble salt,

4-N-methyl-N-acetoxyethylamino-3-phenoxy benzene diazonium chloride,zinc chloride double salt,

4 di 2'-acetoxyethylamino-3-p-chlorophenoxy-6-chlorobenzene diazoniumchloride, zinc chloride double salt,

4 di-propionyloxyethylamino-3-p-chlorophenoxy-6-chlorobenzenediazoniumchloride, zinc chloride double salt,

4-di-2'-chloroethylamino 3 phenoxybenzene diazonium sulphate,

4 N-methyl-N-p-chlorobenzylaminc-3-p-methyl-phenoxybenzene diazoniumchloride, zinc chloride double salt.

4 morpholino-3pchlorophenoxy-6-bromobenzenediazonium chloride, zincchloride double salt,

4 N methyl-N-cyclohexylamino-3-p-chlorophenoxy-6- chlorobenzencdiazoniumsulphate,

4-di(phenylamidocarbonyloxyethyl)amino 3 p-chlorophenoxy 6 chlorobenzenediazonium chloride, zinc chloride double salt,

4-di(ethoxycarbonyloxyethyl)amino-3-p chlorophenoxyfi-chlorobenzenediazonium chloride, zinc chloride double salt,

4-'di(acetyloxyethyl)amino-3-2-,4',5' trichlorophenoxy- '6-cholrobenzenediazonium chloride, zinc chloride double salt,

4-di(phenacetyloxyethyl)amino-3-p chlorophenoxy 6- chlorobenzenediazonium chloride, zinc chloride double salt,

4-di(benzoyloxyethyl)amino-3-p-chlorophenoxy-6 chlorobenzene diazoniumchloride, zinc chloride double salt,

4-di(furoyl(2)oxyethyl)amino-3-p chlorophenoxy 6- chlorobenzenediazonium chloride, zinc chloride double salt,

4-di(chloroacetyloxyethyl)amino-3-p-chlorophenoxy 6- chlorobenzenediazonium chloride, zinc chloride double salt,

4-di(methylsulphonyloxyethyl)amino 3 p chlorophenoxy-6-chlorobenzenediazonium chloride, zinc chloride double salt.

The diazotype material according to the invention may of course alsocontain mixtures of diazo compounds.

However, the use of a mixture containing a diazo compound which uponexposure yields light-decomposition products which form dyestuffs withundesirable shades owing to reaction with a diazo compound present inthe mixture, is preferably avoided.

para-position with respect to the tertiary amino group.

The nitroso or nitro compound or the azo-dyestuif thus obtained isreduced to an amino compound, and this amino compound is converted intoa diazonium compound by treatment with nitrous acid. The diazoniumcompound can be obtained as a double salt, e.g. by precipitation withzinc chloride, cadmium chloride, p-chlorobenzene sulphonic acid, sodiumborofiuoride and the like.

Forthe preparation of diazo compounds having a substituent such as achlorine atom in the para-position with respect to the phenoxy orsubstituted phenoxy group, the

. starting material is p-chloro o-nitro chlorobenzene.

With regard to the alkylation and aralkylation referred to above, it isobserved that hydrogen atoms of the alkyl and/or the aralkyl groups maybe replaced by substituents such as hydroxy and methyl groups andchlorine atoms.

The following examples will serve to illustrate the invention:

Example I White base-paper of Weight 80 g./m. as used for the diazotypeprocess is sensitized with a solution of:

4-N-methyl-N-benzylamino-3 phenoxybenzene diazonium chloride, zincchloride double salt g 23 6 Citric acid g 15 Polyvinyl acetatedispersion, Vinnapas H.60 cm. 20

in 1000 cm. of water and dried.

The sensitized surface contains approximately 0.45 millimole of diazocompound per m The light-sensitive side of a sheet of the diazotypepaper thus prepared is covered with a sheet of tracing paper, on which apencil drawing has been made, and exposed in an exposure apparatusequipped with actinically fluorescent low-pressure mercury-vapour lamps.Exposure is continued until in the portions which are in contact withthe blank parts of the drawings a small quantity or diazo compound isstill left. The amount at which the exposure has to be terminated can bedetermined very well by visual observation (e.g. from the direction ofthe light-source) of the change of colour which occurs in thelight-sensitive layer during the exposure. This moment is soon reached.

The latent diazotype copy thus obtained is developed by treating it witha developing liquid of the following composition:

Grams Thiourea 25 2,3-hydroxynaphthoic acid fl-hydroxy ethylamide 18Dibutylnaphthalene sulphonic acid sodium salt, commercially availableunder the name of Sorbit P 1.5 Mannitol 20 Potassium tetraborate (5 aq.)74

Potassium hydroxide 12.6 in 1000 cm. of water.

The developed copy shows a violet-coloured image on uniformly foggybackground which is also violetcoloured. The violet azo-dyestuff ishighly resistant to a decrease of the pH.

If, instead of the above-mentioned diazo compound, a corresponding diazocompound having an alkoxy group instead of the phenoxy group is used, ablue-violet image on a foggy background having a grey-brown violetolfshade is obtained.

The diazo compound used according to this example is prepared asfollows:

2-aminodiphenylether is benzylated and then methylated. The o-phenoxyN-benzyl N-methylaniline thus obtained (boiling point mm l94l97 C.) isnitrated, after which the p-nitro-o-phenoxy-N-benzyl-N-methylaniline isreduced and converted into the diazo compound in the usual way.

Example II White base-paper of Weight g./m. as used for the diazotypeprocess is sensitized with a solution of:

4 N methyl N benzylamino-3-p-chlorophenoxy- 6-chlorobenzene diazoniumchloride, zinc chloride double salt g 27 Tartaric acid g-.. 4 Boric acidg 1 Polyvinyl acetate dispersion, Vinnapas H.60 cm. 20

Grams Thiourea 15 Phloroglucinol 4 Z-ethylhexyl sulphuric acidmono-ester as sodium salt (commercially available under the name ofTergitol 08) 1.2

Grams Benzoic acid 2.5 Sodium benzoate 15 Sodium formate 150 in 1000 cm.of water. I

The pH of the developing liquid is about 5.9.

Within some tens of seconds after the application of the layer ofdeveloping liquid the developed copy shOWS a black image on a uniformlyfoggy gray-coloured background. The azo-dyestulf in the foggy backgroundhas the same colour as that in the black image portions. The blackazo-dyestulf is highly resistant to a decrease of the pH.

If, instead of the above-mentioned diazo compound a corresponding diazocompound having an alkoxy group instead of the p-chlorophenoxy group isused, a black image on a foggy background having a red-brown offshade isobtained.

The diazo compound used according to this example is prepared asfollows:

2-p-chlorophenoxy-5-chloroaniline (commercially available under the nameof Echtrot F.R. base) is benzylated. The product thus obtained has amelting range between 78 and 80 C. It is methylated to2-p-chlorophenoxy-S-chloro- N-methyl-N-benzyl-aniline, which is nitratedto 2-p-chlorophenoxy-4-nitro-5 chloro N methyl-N-benzylaniline (paleyellow crystals, melting point 102 C.). This compound is reduced andconverted into the diazo compound in the usual way.

When, instead of 2 7 g. of 4-N-methyl-N-benzylamino3-p-chlorophenoxy-6-chlorobenzene diazonium chloride, zinc chloridedouble salt, 30 g. of 4-dirnethylamino 3-0,p-dichlorophenoxy-6-chlorobenzene diazonium chloride, zinc chloridedouble salt, is used in the sensitizing liquid,

a copy with a black image on a grey foggy background is' also obtained,which does not show off-shades and the azo-dyestuif of which is highlyresistant to acid.

The latter compound is prepared as follows:

2.5 dichloronitrobenzene is converted into2-o,pdichlorophenoxy--chloronitrobenzene (melting point 85 C.) by fusionwith 2.4-dichlorophenol and potassium hydroxide in the presence ofcopper powder. This compound is reduced catalytically, after which theamino compound thus obtained is methylated to2-o,p-dichlorophenoxy-S-chlorodirnethylaniline (boiling point 25 mm,188-192" C.). This compound is nitrated to2-o,pdichlorophenoxy-S-chloro-4-nitro dimethylaniline, which compound isreduced and converted into the diazo compound in the usual way.

Example III 4 N methyl N-benzylamine S-p-chlorophenoxybenzenediazoniumchloride, zinc chloride double salt g 28 Citric acid g 5Ethanol, 96% cm. 250 Water m 750 The excess of liquid is squeezed offand the sensitized layer is dried. It contains approximately 0.9millimole of diazo compound per 111.

A sheet of the diazotype material thus prepared is imagewise exposed asdescribed in Example I. The endpoint of the exposure can be observedvery well; it is reached very soon.

The latent diazotype copy thus obtained is developed by treating itsimage surface with a developing liquid of the following composition:

N-methyl-4-hydroxyquinolone-2 Isopropylnaphthalene sulphonic acid assodium salt 2 Sorbitol 25 Potassium tetraborate (5 aq.) 74 Potassiumhydroxide 12.6

in 1000 cm. of water.

The developed copy shows a strong red image on a uniformly foggybackground having the same red colour. The red azo-dyestuff is highlyresistant to a decrease of the pH. Upon. being wetted with a liquid withpH 2, it does not change its colour.

When, instead of the above-mentioned diazo compound, a correspondingdiazo compound having an alkoxy group instead of the p-c hlorophenoxygroup is used, a red-violet image is obtained, the colour of whichchanges to yellow upon treatment with the said liquid with pH 2.

The diazo compound used according to this example is prepared asfollows:

By reaction of o-nitro chlorobenzene with p-chlorophenol in an alkalinemedium at about C., 2-nitro-4- chloro diphenyl ether is prepared, whichis reduced to 2- amino-4'-chlorodiphenylether. This product ismethylated to 2 p chlorophenoxy-N,N-dimethylaniline (boiling point 13 mm187 C.) This compound is nitrated and the 4-nitro2-p-chlorophenoxy-N,N-dimethylaniline thus obtained is reduced andconverted into the diazo compound in the usual way.

Example IV White base-paper of weight 80 g./m. as used for the diazotypeprocess is sensitized with a solution of: 4-di(acetoxyethyl)amino-3-p-chlorophenoxy-6-chlorobenzene diazonium chloride zinc chloridedouble salt g 36 Tartaric acid g 5 1,3,6-naphthalene trisulphonic acidsodium salt g 30 Polyvinylacetate dispersion Vinnapas H.60 cm. 30 in1000 cm. of water and dried.

The sensitized surface contains approximately 0.5 millimole of diazocompound per m. The diazotype paper has good keeping qualities.

A sheet of the diazotype paper is image-wise exposed as described inExample I. The endpoint of the exposure can be observed very well; it isreached very soon.

The latent diazotype copy thus obtained is developed by applying on itsimage-surface a layer of approximately 8 g./m. of a developing liquid ofthe following composition:

Grams Thiourea 10 Phloroglucinol 6.5 Resorcinol 4 Z-ethylhexylsulphuricacid mono-ester as sodium salt 1.2 Sodium formate 14 Sodium benzoate 22Sodium citrate (2 aq.) 47 Citric acid 1.2

in 1000 cm. of water.

9 When a sheet of the diazotype paper according to this example isimage-wise exposed and developed-with a developing liquid of thefollowing composition:

Grams Thiourea 31 Phloroglucinol 6.5 Resorcinol 6.5 Isopropylnaphthalenesulphonic acid sodium salt 2 Sorbitol 5 Saccharose 15 Potassiumtetraborate (5 aq.) 53 Potassium hydroxide 9 White base-paper suitablefor the diazotype process, of 80 g./m. weight, is sensitized with asolution of:

4-dimethylamino 3-phenoxy 6-chlorobenzene diazonium chloride, zincchloride double salt g 17 4-(4-methylphenyl) mercapto2,5-di-n-propoxybenzene diazonium chloride, zinc chloride double salt g1.8 Tartaric acid g 3.5 Boric acid g 1.5 Polyvinyl acetate dispersionVinnapas H.60 cm. 30

in 1000 cm. of water and dried.

The sensitized surface contains approximately 0.46 millimole of diazocompound per m. about 92% is formed by the main component of the mixtureof diazo compounds.

A sheet of the diazotype paper is image-wise exposed as described inExample I. The endpoint of the exposure can be clearly observed; it isreached very soon.

The latent diazotype copy thus obtained is developed by applying on itsimage surface a layer of approximately 8 g./m. of a developing liquid ofthe following composition:

Grams Thiourea 10 Phloroglucinol 4 Sulphonated succinic aciddi-isobutylester (commercially available under the trade name of AerosolIB) 3 Citric acid 1 Sodium benzoate 25 Tertiary sodium citrate (5 aq.)100 in 1000 cm. of water.

The pH of the developing liquid is about 6.3.

The developed copy shows a black image on a uniformly foggy background.The image becomes visible considerably sooner than when, instead of theabove-mentioned mixture of diazo compounds, exclusively 20.6 g. of themain component is used in the sensitizing liquid. The azodyestutf in thefoggy background has the same colour as that in the black imageportions. The black azo-dyestulf is highly resistant to a decrease ofthe pH.

If the base-paper has a smooth surface and the developing liquid isapplied with the aid of a roller rotating in a direction opposite tothat of the movement of the copy, the developed image may show somebleeding owing to the movement, during the development, of molecules ofthe diazo compound forming the main component of the mixture. Inconsequence of this bleeding the azo-dyestufi portions show a non-sharpboundary in the form of an edge of clearly visible feathering varying inlength between a few tenths of a millimetre and a few millimetres. Thisedge is completely absent, or much shorter, or much less visible, whenthe phenoxy group in the diazo compound forming the main component ofthe mixture carries a chlorine atom as substituent.

What we claim is:

1. A one-component diazotype material comprising a support sensitizedwith a light-sensitive composition containing, in the absence of an azocoupling component, a light-sensitive diazo compound of the formula /R:XNg N in which is selected from the class consisting of dialkylaminogroups, N-alkyl-N-benzylamino groups, N-alkyl-N-cyclohexylamino groups,(alkyl)(acyloxyalkyl)amino groups, di(acyloxyalkyl)amino groups and themorpholino ring,

R is a phenyl group,

X is an anion, and

Y is selected from the class consisting of hydrogen and halogen atoms.

2. A one-component diazotype material according to claim 1, wherein oneof R and R is a benzyl group.

3. A one-component diazotype material according to claim 1, wherein eachof R and R is an alkyl group containing at most 2 carbon atoms.

4. A one-component diazotype material according to claim 1, wherein atleast one of R and R is an acyloxyalkyl group.

5. A one-component diazotype material according to claim 1, wherein Y isa chlorine atom.

6. A one-component diazotype material according to claim 1, wherein R isa phenyl group.

7. A one-component diazotype material according to claim 1, wherein R isa chloro-phenyl group.

8. A one-component diazotype material according to claim 1, wherein eachof R and R is an alkyl group containing at most 2 carbon atoms, R is achloro-phenyl group, and Y is a chlorine atom.

9. l-diazo 4-(di-alkylamino) 3-phenoxy benzene compounds.

10. l-diazo 4-(di-alkylamino) 3 (4 chlorophenoxy) 6-chloro benzene.

11. l-diazo 4-dimethylamino 3 (4' chlorophenoxy) 6-chlorobenzene.

12. l diazo 4 diethylamino 3 (4' chlorophenoxy) 6-chlorobenzene.

13. l-diazo 4-di(acetyloxyethyl)amino 3 (4' chlorophenoxy)6-chlorobenzene.

14. A one-component diazotype material comprising a support sensitizedwith a light-sensitive composition containing, in the absence of an azocoupling component, a light-sensitive l-diazo 4-dimethylamino 3-phenoxybenzene.

15. A one-component diazotype material comprising a support sensitizedwith a light-sensitive composition containing, in the absence of an azocoupling component, a light-sensitive l-diazo 4-(methyl) (benzyl) amino3-phenoxy benzene.

16. A one-component diazotype material comprising a support, sensitizedwith a light-sensitive composition containing, in the absence of an azocoupling component, a

1 1 light-sensitive l-diazo 4-di(-acetoxyethyl) amino 3-p-chlorophenoxy6-chlorobenzene.

17. A one-component diazotype material comprising a support sensitizedwith a light-sensitive composition containing, in the absence of an azocoupling component, a light-sensitive l-diazo 4-dialkyl amino3-p-chlorophenoxy 6-chlorobenzene in which the alkyl groups each containat most 2 carbon atoms.

18. A one-component diazotype material comprising a support sensitizedwith a light-sensitive composition containing, in the absence of an azocoupling component, a light-sensitive l-diazo 4-dimethylamino3-p-chlorophenoxy 6-chlor0benzene.

19. A process for the production of a diazotype print which comprisesimagewise exposing to actinic light a diazotype material as defined inclaim 1 and developing the exposed material by applying to it a film ofa liquid developer containing phloroglucinol.

20. A process for the production of a diazotype print diazotype materialas defined in claim 15 and developing the exposed material by applyingto it a film of a weakly acid liquid developer containingphloroglucinol.

References Cited UNITED STATES PATENTS 2,405,523 8/1946 Sease et al96---91 3,169,869 2/ 1965 Hendrick 96 91 FOREIGN PATENTS 528,606 7/1931Germany. 865,451 2/ 1953 Germany. 425,235 3/ 1935 Great Britain. 564,3432/ 1958 Belgium.

OTHER REFERENCES Chemical Abstracts, vol. 46, p. 3510a, April 1952.

NORMAN G. TORCHIN, Primary Examiner.

which comprises imagewise exposing to actinic light a 20 CL BOWERS,JR-,Assismnt Examiner-

1. A ONE-COMPONENT DIAZOTYPE MATERIAL COMPRISING A SUPPORT SENSITIZEDWITH A LIGHT-SENSITIVE COMPOSITION CONTAINING, IN THE ABSENCE OF AN AZOCOUPLING COMPONENT, A LIGHT-SENSITIVE DIAZO COMPOUND OF THE FORMULA 19.A PROCESS FOR THE PRODUCTION OF A DIAZOTYPE PRINT WHICH COMPRISESIMAGEWISE EXPOSING TO ACTINIC LIGHT A DIAZOTYPE MATERIAL AS DEFINED INCLAIM 1 AND DEVELOPING THE EXPOSED MATERIAL BY APPLYING TO IT A FILM OFA LIQUID DEVELOPER CONTAINING PHLOROGLUCINOL.